Liquid crystal writing device, writing board, blackboard and drawing board for two-color writing display

Abstract

The application provides a liquid crystal writing device, a writing board, a blackboard and a drawing board for bicolor writing display, comprising a first PET transparent film, a first polymer composite liquid crystal coating, a polymer transparent layer, a second polymer composite liquid crystal coating and a second PET transparent film arranged in layers in sequence; wherein the first side of the first PET transparent film is plated with ITO, and the second side of the second PET transparent film is plated with ITO; the application is divided into two liquid crystal layers, and the coexistence of two writing colors is realized by adjusting the content of chiral compounds, the content of polymerizable monomers and the content of liquid crystals in each polymer composite liquid crystal layer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of liquid crystal writing, in particular to a liquid crystal writing device for dual-color writing display, a writing board, a blackboard and a drawing board. BACKGROUND

[0002] The statements in this section merely provide background information related to the present application and do not necessarily constitute the prior art.

[0003] The liquid crystal writing board is an important application in the field of liquid crystals, but the single color of writing and the limitation of the preparation method greatly restrict its application environment.

[0004] The inventor found that the traditional writing board is obtained by rolling a film material of a certain thickness, and then using ultraviolet light for polymerization. One of the defects of this method is that when there are uneven parts in the film material, it is difficult to homogenize them in some way, and only the part can be removed, which increases the preparation cost and wastes resources. In addition, due to the design of the layer structure, the traditional writing board only has one color of writing, and the single color greatly hinders its application range. SUMMARY

[0005] In order to solve the problems of the prior art, the present application provides a liquid crystal writing device for dual-color writing display, a writing board, a blackboard and a drawing board, which are divided into two liquid crystal layers. By adjusting the content of chiral compounds, the content of polymerizable monomers and the content of liquid crystals in each polymer composite liquid crystal layer, the coexistence of two writing colors is realized.

[0006] In order to achieve the above purpose, the present application adopts the following technical scheme:

[0007] The first aspect of the present application provides a liquid crystal writing device for dual-color writing display.

[0008] A liquid crystal writing device for dual-color writing display, comprising a first PET transparent film, a first polymer composite liquid crystal coating layer, a polymer transparent layer, a second polymer composite liquid crystal coating layer and a second PET transparent film arranged in layers in sequence.

[0009] The first side of the first PET transparent film is plated with ITO, and the second side of the second PET transparent film is plated with ITO.

[0010] As an optional implementation, the first polymer composite liquid crystal coating layer is uniformly distributed on the ITO of the first PET transparent film by means of blade coating, and the second polymer composite liquid crystal coating layer is uniformly distributed on the ITO of the second PET transparent film by means of blade coating.

[0011] As an optional implementation, the first polymer composite liquid crystal coating and the second polymer composite liquid crystal coating both contain left-handed and right-handed voltage tinting agents, and the driving voltage and driving frequency of the two liquid crystal layers are kept the same or different by adjusting the content of the ultraviolet polymerizable monomer, the voltage tinting agent and the nematic liquid crystal in the liquid crystal layer.

[0012] As an optional implementation, the first PET transparent film and the second PET transparent film are doped with an infrared light shielding agent, and the infrared light shielding agent includes 0-10 parts of zinc oxide nanospheres, 0-10 parts of gold sulfide nanospheres and 0-10 parts of copper oxide nanorods.

[0013] As an optional implementation, the raw material composition of the first polymer composite liquid crystal coating includes, by weight fraction, 50-95 parts of nematic liquid crystal, 1-30 parts of a voltage tinting agent mixture, 5-50 parts of an ultraviolet polymerizable monomer mixture, 0.1-10 parts of a photoinitiator mixture, 0.01-1 part of an ultraviolet absorber and 0.05-0.5 parts of a micron-sized spherical spacer.

[0014] As a further limitation, the raw material composition of the voltage tinting agent mixture includes, by weight fraction, 0-10 parts of (R)-(-)-2-pentanol, 0-10 parts of (R)-2-chlorobutyric acid, 0-10 parts of (R)-3-hydroxybutyric acid methyl ester, 0-10 parts of (S)-(+)-2-butanol, 0-10 parts of (S)-2-chloro-3-methylbutyric acid and 0-10 parts of (S)-2-chloro-4-methylvaleric acid, and each component is not zero at the same time.

[0015] As a further limitation, the raw material composition of the ultraviolet polymerizable monomer mixture includes, by weight fraction, 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of dibromotolyl glycidyl ether, 0-30 parts of polydipentaerythritol hexaacrylate, 0-30 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethyloxetane diacrylate, 0-30 parts of cyclotrimethylolpropane formal acrylate, and each component is not zero at the same time.

[0016] As a further limitation, the composition of the photoinitiator mixture includes, by weight fraction, 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, and each component is not zero at the same time.

[0017] As a further limitation, the raw material composition of the ultraviolet absorber includes, by weight parts: 0-1 part of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0-1 part of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 0-1 part of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, each component not being 0 at the same time.

[0018] As a further limitation, the microspherical spacer is: 0-0.5 parts of cross-linked polyacrylic acid microspheres, 0-0.5 parts of cross-linked polymethyl methacrylate microspheres, 0-0.5 parts of cross-linked PEG microspheres, 0-0.5 parts of silica microspheres, and 0-0.5 parts of alumina microspheres, each microspherical spacer not being 0 at the same time.

[0019] As an optional implementation, the raw material composition of the second polymer composite liquid crystal coating includes, by weight parts: 50-95 parts of nematic liquid crystal, 1-30 parts of voltage toner mixture, 5-50 parts of ultraviolet polymerizable monomer mixture, 0.1-10 parts of photoinitiator mixture, 0.01-1 part of ultraviolet absorber, and 0.05-0.5 part of microspherical spacer.

[0020] As a further limitation, the raw material composition of the voltage toner mixture includes, by weight parts: 0-10 parts of (R)-(-)-2-pentanol, 0-10 parts of (R)-2-chlorobutyric acid, 0-10 parts of (R)-3-hydroxybutyric acid methyl ester, 0-10 parts of (S)-(+)-2-butanol, 0-10 parts of (S)-2-chloro-3-methylbutyric acid, 0-10 parts of (S)-2-chloro-4-methylvaleric acid, each component not being 0 at the same time.

[0021] As a further limitation, the raw material composition of the ultraviolet polymerizable monomer mixture includes, by weight parts: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of dibromotolyl glycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, 0-30 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethyloxetane diacrylate, 0-30 parts of cyclotrimethylolpropane formal acrylate, each component not being 0 at the same time.

[0022] As a further limitation, the composition of the photoinitiator mixture includes, by weight parts: 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl-p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, each component being different from 0.

[0023] As a further limitation, the raw material composition of the ultraviolet absorber includes, by weight parts: 0-1 part of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0-1 part of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 0-1 part of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, each component being different from 0.

[0024] As a further limitation, the micron-sized spherical spacers are 0-0.5 parts of cross-linked polyacrylic acid microspheres, 0-0.5 parts of cross-linked polymethyl methacrylate microspheres, 0-0.5 parts of cross-linked PEG microspheres, 0-0.5 parts of silica microspheres, and 0-0.5 parts of alumina microspheres, each micron-sized spherical spacer being different from 0.

[0025] As an optional implementation, the polymer transparent layer is formed by phase separation of monomers with small density and monomers with large density in the first polymer composite liquid crystal coating, and the raw material composition of the polymer transparent layer includes, by weight parts: 5-50 parts of an ultraviolet polymerizable monomer mixture and 0.1-10 parts of a photoinitiator mixture.

[0026] As a further limitation, the composition of the ultraviolet polymerizable monomer mixture includes, by weight parts: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, and 0-30 parts of neopentyl glycol polymethyloxetane diacrylate, each component being different from 0.

[0027] As a further limitation, the composition of the photoinitiator mixture includes, by weight parts: 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl-p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, each component being different from 0.

[0028] The second aspect of the present application provides a liquid crystal writing board, which includes the liquid crystal writing device for dual-color writing display according to the first aspect of the present application.

[0029] The third aspect of the present application provides a liquid crystal blackboard comprising the liquid crystal writing device for dual-color writing display according to the first aspect of the present application.

[0030] The fourth aspect of the present application provides a liquid crystal drawing board comprising the liquid crystal writing device for dual-color writing display according to the first aspect of the present application.

[0031] Compared with the prior art, the present application has the following beneficial effects:

[0032] 1. The liquid crystal writing device for dual-color writing display, the writing board, the blackboard and the drawing board according to the present application are divided into two liquid crystal layers, and the coexistence of two writing colors is realized by adjusting the content of chiral compounds, the content of polymerizable monomers and the content of liquid crystals in each polymer composite liquid crystal layer.

[0033] 2. The liquid crystal writing device for dual-color writing display, the writing board, the blackboard and the drawing board according to the present application are prepared by coating to obtain a more uniform liquid crystal layer, and even if there are uneven parts, the coating method can be used to further improve the performance, so that a uniform polymer composite liquid crystal layer is finally obtained, and the performance of the liquid crystal writing device is improved.

[0034] The advantages of the additional aspects of the present application will be partially given in the following description, partially will become obvious from the following description, or will be understood by the practice of the present application. BRIEF DESCRIPTION OF DRAWINGS

[0035] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the illustrative embodiments of the present application and their descriptions serve to explain the present application, and do not constitute an improper limitation of the present application.

[0036] Figure 1 Preparation schematic of the liquid crystal writing device for dual-color writing display provided for the first embodiment of the present application Figure 1 ;

[0037] Figure 2 Preparation schematic of the liquid crystal writing device for dual-color writing display provided for the first embodiment of the present application Figure 2 ;

[0038] Figure 3 Preparation schematic of the liquid crystal writing device for dual-color writing display provided for the first embodiment of the present application Figure 3 ;

[0039] 1, first PET transparent film layer; 2, first ITO conductive layer; 3, liquid crystal microdroplet; 4, polymer transparent layer; 5, ultraviolet light; 6, polymer network; 7, second ITO conductive layer; 8, second PET transparent film layer. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0041] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0042] Where there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0043] Example 1:

[0044] like Figure 1 As shown, Embodiment 1 of the present invention provides a liquid crystal writing device for dual-color writing display, which is configured in five layers, including a first PET transparent film as a first layer, a first polymer composite liquid crystal coating as a second layer, a polymer transparent layer (formed from polymerizable monomers) as a third layer, a second polymer composite liquid crystal coating as a fourth layer, and a second PET transparent film as a fifth layer, which are sequentially configured in layers.

[0045] The first side of the first PET transparent film is coated with ITO, and the second side of the second PET transparent film is coated with ITO.

[0046] The liquid crystal writing device consists of two liquid crystal layers, a second layer and a fourth layer. Both liquid crystal layers are uniformly distributed on two transparent PET films by a scraping method and then cured by photopolymerization.

[0047] After the polymer composite liquid crystal layer is left to stand, phase separation will occur due to differences in density and solubility. By photopolymerization, it can be cured to obtain a transparent polymer layer, which can be separated by two polymer composite liquid crystal layers.

[0048] Both liquid crystal layers contain both left-handed and right-handed voltage toners. By adjusting the content of ultraviolet polymerizable monomers, voltage toners, and nematic liquid crystals in the liquid crystal layers, the driving voltage and driving frequency of the two liquid crystal layers can be kept the same or different. A certain amount of infrared light shielding material is doped into the two PET transparent films coated with ITO on one side to improve some of the performance of the writing board.

[0049] The thickness of the first PET transparent film 1 (first layer) and the second PET transparent film 5 (fifth layer) are 15-70 μm, the light transmittance is 90-97%, and the resistivity is 1-450 Ω / cm. They are internally doped with infrared light shielding materials, including 0-10 parts of zinc oxide nanospheres, 0-10 parts of gold sulfide nanospheres, and 0-10 parts of copper oxide nanorods.

[0050] The first PET transparent film 1 of the first layer is doped with a certain amount of zinc oxide nanospheres, gold sulfide nanospheres and copper oxide nanorods to shield part of the infrared light and improve the sensitivity and selectivity of the writing board.

[0051] The raw material composition of the polymer transparent layer 3 of the second layer includes, by weight fraction: 50-95 parts of nematic liquid crystal, 1-30 parts of voltage toner mixture, 5-50 parts of ultraviolet polymerizable monomer mixture, 0.1-10 parts of photoinitiator mixture, 0.01-1 parts of ultraviolet absorber, and 0.05-0.5 parts of micron-sized spherical spacers.

[0052] The thickness of the second layer of the polymer composite liquid crystal layer is 1-40 μm, the threshold voltage V th is 5-12 V, the saturation voltage V sat is 5-12 V.

[0053] The birefringence of the nematic liquid crystal is 0.2-0.6, the dielectric constant is 26-38, the viscosity value is 1-35 mm 2 ·S -1 , the clearing point is 20-80℃, the molecular weight is 200-1000 g / mol, and the freezing temperature range is -20-20℃.

[0054] The raw material composition of the voltage toner mixture includes, by weight fraction: 0-10 parts of (R)-(-)-2-pentanol (CAS number: 31087-44-2), 0-10 parts of (R)-2-chlorobutyric acid (CAS number: 54053-45-1), 0-10 parts of (R)-3-hydroxybutyric acid methyl ester (CAS number: 3976-69-0), 0-10 parts of (S)-(+)-2-butanol (CAS number: 4221-99-2), 0-10 parts of (S)-2-chloro-3-methylbutyric acid (CAS number: 26782-74-1), and 0-10 parts of (S)-2-chloro-4-methylvaleric acid (CAS number: 28659-81-6), each component is not zero at the same time.

[0055] The raw material composition of the ultraviolet polymerizable monomer mixture comprises, by weight fraction, 0-30 parts of trimethylolpropane triglycidyl ether (CAS No. 30499-70-8), 0-30 parts of resorcinol diglycidyl ether (CAS No. 101-90-6), 0-30 parts of 4-tert-butylphenyl glycidyl ether (CAS No. 3101-60-8), 0-30 parts of neopentyl glycol diglycidyl ether (CAS No. 17557-23-2), 0-30 parts of dibromomethylphenyl glycidyl ether (structural formula as follows), 0-30 parts of polydi-pentaerythritol hexaacrylate (CAS No. 29570-58-9), 0-30 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide (structural formula as follows), 0-30 parts of neopentyl glycol polymethylol polyethylene oxide diacrylate (CAS No. 84170-74-1), 0-30 parts of cyclotrimethylolpropane formal acrylate (structural formula as follows), and each component is not 0 at the same time.

[0056]

[0057] Dibromomethylphenyl glycidyl ether

[0058]

[0059] α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]]-polyethylene oxide

[0060]

[0061] Cyclotrimethylolpropane formal acrylate

[0062] The composition of the photoinitiator mixture comprises, by weight fraction, 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone (CAS No. 68400-54-4), 0-10 parts of ethyl p-dimethylaminobenzoate (CAS No. 10287-53-3), 0-10 parts of benzophenone (CAS No. 119-61-9), 0-10 parts of triphenylsulfonium hexafluorophosphate (CAS No. 57835-99-1), 0-10 parts of tetraethyl Michler's ketone (CAS No. 90-93-7), and each component is not 0 at the same time.

[0063] The raw material composition of the ultraviolet absorber comprises, by weight fraction, 0-1 part of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0-1 part of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), and 0-1 part of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (CAS No.: 3147-75-9), and each component is not 0 at the same time.

[0064] The microspherical spacer is 0-0.5 part of cross-linked polyacrylic acid microspheres, 0-0.5 part of cross-linked polymethyl methacrylate microspheres, 0-0.5 part of cross-linked PEG microspheres, 0-0.5 part of silica microspheres, and 0-0.5 part of alumina microspheres, and each microspherical spacer is not 0 at the same time, and the size of the microspheres is between 1-40 mu m.

[0065] The present application uses voltage toner: (R)-(-)-2-pentanol, (R)-2-chlorobutyric acid, (R)-3-hydroxybutyric acid methyl ester, (S)-(+)-2-butanol, (S)-2-chloro-3-methylbutyric acid, (S)-2-chloro-4-methylvaleric acid, and the use of these voltage toner compounds is less, and at the same time, the voltage toner of left-handed and right-handed is contained, and by controlling the type and amount of different optical activity voltage toner, the purpose of controlling the color of the writing is realized.

[0066] The present application uses ultraviolet polymerizable monomer: 2-dodecyl acrylate, 2-phenoxyethyl acrylate, pentaerythritol tetraacrylate, butyl methacrylate, hydroxypropyl methacrylate, polydiquintetra glycol hexaacrylate, alpha, alpha'-[(1-methylethylidene) bis-4,1-phenylene] bis[omega-[(2-acryloyl) oxy]-polyethylene oxide, neopentyl glycol polymethyl polyethylene oxide dipropylene acrylate, and cyclotrimethylolpropane methyl acetal acrylate, and the application of these ultraviolet polymerizable monomers in the field of writing board is less.

[0067] The present application uses photoinitiator: 2-hydroxy-2-methyl-1-[4-(tert-butyl) phenyl]-1-propanone, ethyl p-dimethylaminobenzoate, benzophenone, triphenylsulfonium hexafluorophosphate, and tetraethyl Michler's ketone, and the application of these photoinitiators in the field of writing board is less.

[0068] The present application controls the driving voltage and driving frequency of the liquid crystal layer by controlling the type and content of the voltage toner, the ultraviolet polymerizable monomer, and the microspherical spacer in the liquid crystal layer.

[0069] The polymerizable monomer mixture of the present application contains monomers with smaller density, which can spontaneously and uniformly float on the monomers with larger density by controlling the proportion, thereby forming another thin layer, and the two polymer composite liquid crystal layers can be well separated.

[0070] In the embodiment, the raw material composition of the second polymer composite liquid crystal coating of the fourth layer includes, by weight fraction: 50-95 parts of nematic liquid crystal, 1-30 parts of voltage toner mixture, 5-50 parts of ultraviolet polymerizable monomer mixture, 0.1-10 parts of photoinitiator mixture, 0.01-1 part of ultraviolet absorber, and 0.05-0.5 part of micron-sized spherical spacer.

[0071] The fourth layer polymer composite liquid crystal layer has a thickness of 1-40 μm, a threshold voltage Vth of 5-12 V, and a saturation voltage Vsat of 5-12 V.

[0072] The nematic liquid crystal has a birefringence of 0.2-0.6, a dielectric constant of 26-38, a viscosity value of 1-35 mm2·S-1, a clearing point of 20-80℃, a molecular weight of 200-1000 g / mol, and a freezing temperature range of -20-20℃.

[0073] The raw material composition of the voltage toner mixture includes, by weight fraction: 0-10 parts of (R)-(-)-2-pentanol, 0-10 parts of (R)-2-chlorobutyric acid, 0-10 parts of (R)-3-hydroxybutyric acid methyl ester, 0-10 parts of (S)-(+)-2-butanol, 0-10 parts of (S)-2-chloro-3-methylbutyric acid, and 0-10 parts of (S)-2-chloro-4-methylvaleric acid, and each component is not 0 at the same time.

[0074] The raw material composition of the ultraviolet polymerizable monomer mixture includes, by weight fraction: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of dibromotolyl glycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, 0-30 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-propenoyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethylol polyethylene oxide diacrylate, and 0-30 parts of cyclotrimethylolpropane methylal acrylate, and each component is not 0 at the same time.

[0075] The composition of the photoinitiator mixture comprises, by weight fraction, 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, and 0-10 parts of tetraethyl Michler's ketone, and each component is not 0 at the same time.

[0076] The raw material composition of the ultraviolet absorber comprises, by weight fraction, 0-1 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0-1 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), and 0-1 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole (CAS No.: 3147-75-9), and each component is not 0 at the same time.

[0077] The micron-level spherical spacers comprise 0-0.5 parts of cross-linked polyacrylic acid microspheres, 0-0.5 parts of cross-linked polymethyl methacrylate microspheres, 0-0.5 parts of cross-linked PEG microspheres, 0-0.5 parts of silica microspheres, and 0-0.5 parts of alumina microspheres, and each micron-level spherical spacer is not 0 at the same time, and the size of the microspheres is between 1-40 mu m.

[0078] The present application uses voltage toner: (R)-(-)-2-pentanol, (R)-2-chlorobutyric acid, (R)-3-hydroxybutyric acid methyl ester, (S)-(+)-2-butanol, (S)-2-chloro-3-methylbutyric acid, (S)-2-chloro-4-methylvaleric acid, and the use of these voltage toner compounds is less, and at the same time, the voltage toner of left-handed and right-handed is contained, and by controlling the type and amount of voltage toner of different optical activity, the purpose of controlling the color of the writing is achieved.

[0079] The present application uses ultraviolet polymerizable monomers: 2-dodecyl acrylate, 2-phenoxyethyl acrylate, pentaerythritol tetraacrylate, butyl methacrylate, hydroxypropyl methacrylate, polydipentaerythritol hexaacrylate, 0-30 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-acryloyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethyl polyethylene oxide dipropyl acrylate, 0-30 parts of cyclo-trihydroxymethyl propane formaldehyde acrylate, and the application of these ultraviolet polymerizable monomers in the field of writing board is less.

[0080] The present application uses photoinitiators: 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, ethyl p-dimethylaminobenzoate, benzophenone, triphenylsulfonium hexafluorophosphate, tetraethyl Michler's ketone, and the application of these photoinitiators in the field of writing board is less.

[0081] The present application controls the driving voltage and driving frequency of the liquid crystal layer by controlling the voltage colorant, the ultraviolet polymerizable monomer and the kind and content of the micron-sized spherical spacer in the liquid crystal layer, so as to keep the same or different driving voltage and driving frequency as the previous layer of liquid crystal.

[0082] In the embodiment, the raw material composition of the polymer transparent layer 3 of the third layer includes, by weight fraction, 5-50 parts of an ultraviolet polymerizable monomer mixture and 0.1-10 parts of a photoinitiator mixture. The layer is formed by phase separation of the smaller monomer and the larger monomer in the upper polymer composite liquid crystal layer of the second layer after light curing;

[0083] The thickness of the polymer transparent layer 3 of the third layer is 1-40 μm, and the light transmittance is 85-95%.

[0084] The composition of the ultraviolet polymerizable monomer mixture includes, by weight fraction, 0-30 parts of trimethylolpropane triglycidyl ether (CAS number: 30499-70-8), 0-30 parts of resorcinol diglycidyl ether (CAS number: 101-90-6), 0-30 parts of 4-tert-butyl phenyl glycidyl ether (CAS number: 3101-60-8), 0-30 parts of neopentyl glycol diglycidyl ether (CAS number: 17557-23-2), 0-30 parts of polydi-pentaerythritol hexaacrylate (CAS number: 29570-58-9), 0-30 parts of neopentyl glycol polymethyloxirane dipropylene acrylate (CAS number: 84170-74-1), and each component is not 0 at the same time.

[0085] The composition of the photoinitiator mixture includes, by weight fraction, 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone (CAS number: 68400-54-4), 0-10 parts of ethyl p-dimethylaminobenzoate (CAS number: 10287-53-3), 0-10 parts of benzophenone (CAS number: 119-61-9), 0-10 parts of triphenylsulfonium hexafluorophosphate (CAS number: 57835-99-1), 0-10 parts of tetraethyl Michler's ketone (CAS number: 90-93-7), and each component is not 0 at the same time.

[0086] The present application uses ultraviolet polymerizable monomers trimethylolpropane triglycidyl ether, resorcinol diglycidyl ether, 4-tert-butyl phenyl glycidyl ether, neopentyl glycol diglycidyl ether, polydi-pentaerythritol hexaacrylate, neopentyl glycol polymethyloxetane diacrylate and photoinitiator 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, ethyl p-dimethylaminobenzoate, benzophenone, triphenylsulfonium hexafluorophosphate, tetraethyl Michler's ketone, which are separated from the first polymer composite liquid crystal coating 2 of the second layer, the first polymer composite liquid crystal coating contains monomers with large density difference, which will produce phase separation after standing, uniformly forming two thin layers, after photocuring, one layer becomes a polymer composite liquid crystal layer, and the other layer becomes a polymer transparent thin layer, wherein the polymer transparent layer can play the role of spacing two liquid crystal layers.

[0087] The preparation process of each layer is as follows:

[0088] (1) Preparation of liquid crystal / ultraviolet polymerizable monomer mixture

[0089] The nematic liquid crystal, voltage toner mixture, ultraviolet polymerizable monomer mixture, photoinitiator mixture, ultraviolet absorber and micron-sized spherical spacer are mixed according to the weight fraction described above to obtain two kinds of uniform and stable liquid crystal / ultraviolet polymerizable monomer mixtures with different proportions;

[0090] (2) Preparation of first polymer composite liquid crystal layer and polymer transparent layer

[0091] Under the conditions of 25-35℃ and vacuum, a layer of 1-15μm thick liquid crystal / ultraviolet polymerizable monomer mixture is uniformly coated on the conductive side of the first layer of PET transparent film by means of blade coating (0.5-10cm·S -1 ) after coating, stand for 5-30min to wait for phase separation, use ultraviolet light with wavelength of 365-398nm and light intensity of 1-100mW / cm 2 for 5-30min to obtain the first polymer composite liquid crystal layer and the polymer transparent layer;

[0092] (3) Preparation of second polymer composite liquid crystal layer

[0093] Under the conditions of 25-35℃ and vacuum, a layer of 1-15μm thick liquid crystal / ultraviolet polymerizable monomer mixture is uniformly coated on the other side of the polymer transparent layer by means of blade coating (0.5-10cm·S -1 ) after coating, the second PET transparent film is attached to the surface of the liquid crystal / ultraviolet polymerizable monomer mixture, and ultraviolet light with wavelength of 365-398nm and light intensity of 1-100mW / cm 2The second polymer composite liquid crystal layer is obtained by irradiating the first polymer composite liquid crystal layer with ultraviolet light for 5-30 minutes.

[0094] The specific preparation process is shown in Figure 1 、 Figure 2 and Figure 3 , wherein 1 is the first PET transparent film layer, 2 is the first ITO conductive layer, 3 is the liquid crystal droplet, 4 is the polymer transparent layer, 5 is the ultraviolet light, 6 is the polymer network, 7 is the second ITO conductive layer, and 8 is the second PET transparent film layer.

[0095] Examples 1-7 give different preparation processes, wherein:

[0096] The preparation process parameters are as follows:

[0097]

[0098]

[0099] PET transparent film parameters:

[0100] Example 1:

[0101] 1) Preparation of the first polymer composite liquid crystal layer and the polymer transparent layer

[0102] The nematic liquid crystal, voltage toner mixture, ultraviolet polymerizable monomer mixture, photoinitiator mixture, ultraviolet absorber, and micron-sized spherical spacer are mixed in the following weight proportions to obtain a uniform and stable liquid crystal / ultraviolet polymerizable monomer mixture;

[0103] The liquid crystal / ultraviolet polymerizable monomer mixture is as follows:

[0104] 60 parts of nematic liquid crystal;

[0105] 3 parts of voltage toner mixture: 0.5 parts of (R)-(-)-2-pentanol, 0.5 parts of (R)-2-chlorobutyric acid, 0.5 parts of (R)-3-hydroxybutyric acid methyl ester, 0.5 parts of (S)-(+)-2-butanol, 0.5 parts of (S)-2-chloro-3-methylbutyric acid, and 0.5 parts of (S)-2-chloro-4-methylvaleric acid;

[0106] 36.84 parts of UV polymerizable monomer mixture: 4 parts of trimethylolpropane triglycidyl ether, 4 parts of resorcinol diglycidyl ether, 4 parts of 4-tert-butylphenyl glycidyl ether, 4 parts of neopentyl glycol diglycidyl ether, 4 parts of dibromophenyl glycidyl ether, 4 parts of polydipentaerythritol hexaacrylate, 4 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyoxirane, 4 parts of neopentyl glycol polymethyloxirane diacrylate, 4.84 parts of cyclotrimethylolpropane formal acrylate;

[0107] 0.1 parts of photoinitiator mixture: 0.02 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.02 parts of ethyl-p-dimethylaminobenzoate, 0.02 parts of benzophenone, 0.02 parts of triphenylsulfonium hexafluorophosphate, 0.02 parts of tetraethyl Michler's ketone;

[0108] 0.01 parts of UV absorber: 0.003 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.003 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.004 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0109] 0.05 parts of micron-sized spherical spacers: 0.01 parts of crosslinked polyacrylic acid microspheres, 0.01 parts of crosslinked polymethyl methacrylate microspheres, 0.01 parts of crosslinked PEG microspheres, 0.01 parts of silica microspheres, and 0.01 parts of alumina microspheres.

[0110] A first layer of PET transparent film was prepared by using a doctor blade (0.5 cm x S -1 ) to uniformly coat a 1 μm thick layer of liquid crystal / UV polymerizable monomer mixture on the conductive side of the first layer of PET transparent film under vacuum at 25°C. After coating, the sample was allowed to stand for 5 min to allow phase separation to occur. The sample was then irradiated with UV light having a wavelength of 365 nm and an intensity of 1 mW / cm 2 for 5 min to obtain a first polymer composite liquid crystal layer and a polymer transparent layer.

[0111] 2) Preparation of a second polymer composite liquid crystal layer

[0112] The nematic liquid crystal, voltage toner mixture, UV polymerizable monomer mixture, photoinitiator mixture, UV absorber, and micron-sized spherical spacers were mixed in the following weight proportions to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0113] The proportions of the liquid crystal / UV polymerizable monomer mixture were as follows:

[0114] 60 parts of nematic liquid crystal;

[0115] 4 parts of voltage tinting agent mixture: 0.7 parts of (R)-(-)-2-pentanol, 0.7 parts of (R)-2-chlorobutyric acid, 0.7 parts of (R)-methyl 3-hydroxybutyrate, 0.7 parts of (S)-(+)-2-butanol, 0.6 parts of (S)-2-chloro-3-methylbutyric acid, and 0.6 parts of (S)-2-chloro-4-methylvaleric acid;

[0116] 35.84 parts of ultraviolet polymerizable monomer mixture: 4 parts of trimethylolpropane triglycidyl ether, 4 parts of resorcinol diglycidyl ether, 4 parts of 4-tert-butylphenyl glycidyl ether, 4 parts of neopentyl glycol diglycidyl ether, 4 parts of dibromophenyl glycidyl ether, 4 parts of polydipentaerythritol hexaacrylate, 4 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-poly(ethylene oxide, 4 parts of neopentyl glycol polymethyloxetane diacrylate, 3.84 parts of cyclotrimethylolpropane formal acrylate;

[0117] 0.1 parts of photoinitiator mixture: 0.02 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.02 parts of ethyl p-dimethylaminobenzoate, 0.02 parts of benzophenone, 0.02 parts of triphenylsulfonium hexafluorophosphate, 0.02 parts of tetraethyl Michler's ketone;

[0118] 0.01 parts of ultraviolet absorber: 0.003 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.003 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.004 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0119] 0.05 parts of micron-sized spherical spacers: 0.01 parts of crosslinked polyacrylic acid microspheres, 0.01 parts of crosslinked polymethyl methacrylate microspheres, 0.01 parts of crosslinked PEG microspheres, 0.01 parts of silica microspheres, and 0.01 parts of alumina microspheres.

[0120] A 1-μm-thick liquid crystal / ultraviolet polymerizable monomer mixture was uniformly coated on the other side of the polymer transparent layer by means of blade coating (0.5 cm·S -1 ) under vacuum at 25°C, and after the coating was completed, a second PET transparent film was attached to the surface of the liquid crystal / ultraviolet polymerizable monomer mixture, and ultraviolet light with a wavelength of 365 nm and an illumination intensity of 1 mW / cm 2 was used to irradiate for 5 min, thereby obtaining a second polymer composite liquid crystal layer.

[0121] Example 2:

[0122] 1) Preparation of the first polymer composite liquid crystal layer and the polymer transparent layer

[0123] A nematic liquid crystal, a voltage tinting agent mixture, a UV polymerizable monomer mixture, a photoinitiator mixture, a UV absorber, and a micron-sized spherical spacer are mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0124] The liquid crystal / UV polymerizable monomer mixture is, for example, as follows:

[0125] 65 parts of a nematic liquid crystal;

[0126] 6 parts of a voltage tinting agent mixture: 1 part of (R)-(-)-2-pentanol, 1 part of (R)-2-chlorobutyric acid, 1 part of (R)-3-hydroxybutyric acid methyl ester, 1 part of (S)-(+)-2-butanol, 1 part of (S)-2-chloro-3-methylbutyric acid, and 0.5 parts of (S)-2-chloro-4-methylvaleric acid;

[0127] 40 parts of a UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydipentaerythritol hexaacrylate, 4 parts of a,a'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyoxirane, 3 parts of neopentyl glycol polymethyloxirane diacrylate, 3 parts of cyclotrimethylolpropane formal acrylate;

[0128] 0.2 parts of a photoinitiator mixture: 0.04 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.04 parts of ethyl p-dimethylaminobenzoate, 0.04 parts of benzophenone, 0.04 parts of triphenylsulfonium hexafluorophosphate, 0.04 parts of tetraethyl Michler's ketone;

[0129] 0.03 parts of a UV absorber: 0.01 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.01 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.01 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0130] 0.1 parts micron-sized spherical spacers: 0.02 parts cross-linked polyacrylic acid microspheres, 0.02 parts cross-linked polymethyl methacrylate microspheres, 0.02 parts cross-linked PEG microspheres, 0.02 parts silica microspheres, and 0.02 parts alumina microspheres.

[0131] The first layer of PET transparent film was uniformly coated with a 3 μm thick layer of liquid crystal / ultraviolet polymerizable monomer mixture on the conductive side of the film using a doctor blade (1 cm s -1 ) at 27°C under vacuum. After the coating was complete, the mixture was allowed to stand for 10 minutes to allow phase separation to occur. The mixture was then irradiated with ultraviolet light having a wavelength of 371 nm and an intensity of 18 mW / cm 2 for 10 minutes to produce a first polymer composite liquid crystal layer and a polymer transparent layer.

[0132] 2) Preparation of a second polymer composite liquid crystal layer

[0133] A nematic liquid crystal, a voltage toner mixture, an ultraviolet polymerizable monomer mixture, a photoinitiator mixture, an ultraviolet absorber, and micron-sized spherical spacers were mixed in the following weight proportions to produce a uniform and stable liquid crystal / ultraviolet polymerizable monomer mixture:

[0134] The liquid crystal / ultraviolet polymerizable monomer mixture had the following proportions:

[0135] 65 parts nematic liquid crystal;

[0136] 8 parts voltage toner mixture: 1 part (R)-(-)-2-pentanol, 1.5 parts (R)-2-chlorobutyric acid, 1.5 parts (R)-3-hydroxybutyric acid methyl ester, 1 part (S)-(+)-2-butanol, 1.5 parts (S)-2-chloro-3-methylbutyric acid, and 1.5 parts (S)-2-chloro-4-methylvaleric acid;

[0137] 38 parts ultraviolet polymerizable monomer mixture: 5 parts trimethylolpropane triglycidyl ether, 5 parts resorcinol diglycidyl ether, 4 parts 4-tert-butylphenyl glycidyl ether, 4 parts neopentyl glycol diglycidyl ether, 4 parts dibromophenyl glycidyl ether, 4 parts polydipentaerythritol hexaacrylate, 4 parts α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 4 parts neopentyl glycol polymethyloxetane diacrylate, 4 parts cyclotrimethylolpropane formal acrylate;

[0138] 0.2 parts photoinitiator mixture: 0.04 parts 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.04 parts ethyl p-dimethylaminobenzoate, 0.04 parts benzophenone, 0.04 parts triphenylsulfonium hexafluorophosphate, 0.04 parts tetraethyl Michler's ketone;

[0139] 0.03 parts of a UV absorber: 0.01 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.01 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.01 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0140] 0.1 parts of micron-sized spherical spacers: 0.02 parts of crosslinked polyacrylic acid microspheres, 0.02 parts of crosslinked polymethyl methacrylate microspheres, 0.02 parts of crosslinked PEG microspheres, 0.02 parts of silica microspheres, and 0.02 parts of alumina microspheres.

[0141] A 3-μm-thick liquid crystal / UV-polymerizable monomer mixture was uniformly coated on the other side of the polymer transparent layer at 27°C under vacuum by means of scraping (1 cm·s -1 ) and, after coating, a second PET transparent film was attached to the surface of the liquid crystal / UV-polymerizable monomer mixture, which was irradiated with UV light having a wavelength of 371 nm and an illumination intensity of 18 mW / cm 2 for 10 min, to obtain a second polymer composite liquid crystal layer.

[0142] Example 3:

[0143] 1) Preparation of a first polymer composite liquid crystal layer and a polymer transparent layer

[0144] A nematic liquid crystal, a voltage toner mixture, a UV-polymerizable monomer mixture, a photoinitiator mixture, a UV absorber, and micron-sized spherical spacers were mixed in the following weight proportions to obtain a uniform and stable liquid crystal / UV-polymerizable monomer mixture:

[0145] The liquid crystal / UV-polymerizable monomer mixture had the following proportions:

[0146] 70 parts of a nematic liquid crystal;

[0147] 10 parts of a voltage toner mixture: 1 part of (R)-(-)-2-pentanol, 1 part of (R)-2-chlorobutyric acid, 1 part of (R)-3-hydroxybutyric acid methyl ester, 1 part of (S)-(+)-2-butanol, 1 part of (S)-2-chloro-3-methylbutyric acid, and 0.5 part of (S)-2-chloro-4-methylvaleric acid;

[0148] 42 parts of UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydi-pentaerythritol hexaacrylate, 4 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-poly(ethylene oxide), 4 parts of neopentyl glycol polymethyloxetane diacrylate, 4 parts of cyclotrimethylolpropane formal acrylate;

[0149] 1 part of photoinitiator mixture: 0.2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.2 parts of ethyl-p-dimethylaminobenzoate, 0.2 parts of benzophenone, 0.2 parts of triphenylsulfonium hexafluorophosphate, 0.2 parts of tetraethyl Michler's ketone;

[0150] 0.5 parts of UV absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.2 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.1 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0151] 0.3 parts of micron-sized spherical spacers: 0.06 parts of crosslinked polyacrylic acid microspheres, 0.06 parts of crosslinked polymethyl methacrylate microspheres, 0.06 parts of crosslinked PEG microspheres, 0.06 parts of silica microspheres, and 0.06 parts of alumina microspheres.

[0152] A first polymer composite liquid crystal layer and a polymer transparent layer were obtained by using a UV light with a wavelength of 376 nm and an illumination intensity of 36 mW / cm -1 ) to irradiate for 15 min after uniformly coating a 7-μm-thick liquid crystal / UV polymerizable monomer mixture on the conductive surface of the first layer of PET transparent film at 29°C under vacuum by means of scraping (3 cm·S 2 ) and then allowing it to stand for 15 min to wait for phase separation.

[0153] 2) Preparation of a second polymer composite liquid crystal layer

[0154] The nematic liquid crystal, voltage toner mixture, UV polymerizable monomer mixture, photoinitiator mixture, UV absorber, and micron-sized spherical spacers were mixed in the following weight proportions to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture.

[0155] The liquid crystal / UV polymerizable monomer mixture had the following proportions by weight:

[0156] 70 parts of nematic liquid crystal;

[0157] 15 parts of voltage tinting agent mixture: 2 parts of (R)-(-)-2-pentanol, 2 parts of (R)-2-chlorobutyric acid, 2 parts of (R)-methyl 3-hydroxybutyrate, 3 parts of (S)-(+)-2-butanol, 3 parts of (S)-2-chloro-3-methylbutyric acid, and 3 parts of (S)-2-chloro-4-methylvaleric acid;

[0158] 42 parts of ultraviolet polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydipentaerythritol hexaacrylate, 4 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 4 parts of neopentyl glycol polymethyloxetane diacrylate, 4 parts of cyclotrimethylolpropane formal acrylate;

[0159] 1 part of photoinitiator mixture: 0.2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.2 parts of ethyl p-dimethylaminobenzoate, 0.2 parts of benzophenone, 0.2 parts of triphenylsulfonium hexafluorophosphate, 0.2 parts of tetraethyl Michler's ketone;

[0160] 0.5 parts of ultraviolet absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.2 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.1 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0161] 0.3 parts of micron-sized spherical spacers: 0.06 parts of crosslinked polyacrylic acid microspheres, 0.06 parts of crosslinked polymethyl methacrylate microspheres, 0.06 parts of crosslinked PEG microspheres, 0.06 parts of silica microspheres, and 0.06 parts of alumina microspheres.

[0162] A 7-μm-thick liquid crystal / ultraviolet polymerizable monomer mixture was uniformly coated on the other side of the polymer transparent layer at 29°C under vacuum by means of doctor blade (3 cm·S -1 ) and, after the coating was completed, a second PET transparent film was attached to the surface of the liquid crystal / ultraviolet polymerizable monomer mixture, which was irradiated with ultraviolet light having a wavelength of 376 nm and an illumination intensity of 36 mW / cm 2 for 15 min to obtain a second polymer composite liquid crystal layer.

[0163] Example 4:

[0164] 1) Preparation of the first polymer composite liquid crystal layer and the polymer transparent layer

[0165] A nematic liquid crystal, a voltage tinting agent mixture, a UV polymerizable monomer mixture, a photoinitiator mixture, a UV absorber, and a micron-sized spherical spacer were mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0166] The liquid crystal / UV polymerizable monomer mixture was, for example, as follows:

[0167] 75 parts of a nematic liquid crystal;

[0168] 15 parts of a voltage tinting agent mixture: 2 parts of (R)-(-)-2-pentanol, 2 parts of (R)-2-chlorobutyric acid, 2 parts of (R)-3-hydroxybutyric acid methyl ester, 3 parts of (S)-(+)-2-butanol, 3 parts of (S)-2-chloro-3-methylbutyric acid, and 3 parts of (S)-2-chloro-4-methylvaleric acid;

[0169] 45 parts of a UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydipentaerythritol hexaacrylate, 5 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-propenoyl)oxy]-polyoxirane, 5 parts of neopentyl glycol polymethyloxirane diacrylate, 5 parts of cyclotrimethylolpropane formal acrylate;

[0170] 3 parts of a photoinitiator mixture: 0.6 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.6 parts of ethyl-p-dimethylaminobenzoate, 0.6 parts of benzophenone, 0.6 parts of triphenylsulfonium hexafluorophosphate, 0.6 parts of tetraethyl Michler's ketone;

[0171] 0.5 parts of a UV absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.2 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.1 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0172] 0.5 parts of a micron-sized spherical spacer: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0173] The liquid crystal / UV polymerizable monomer mixture was coated on a glass substrate at 31°C under vacuum conditions using a doctor blade (5 cm x S -1) in the manner of the first layer of PET transparent film, the conductive surface of the first layer of PET transparent film is evenly coated with a 8 μm thick liquid crystal / UV polymerizable monomer mixture, after the coating is completed, it is left for 18 min to wait for the phase separation, using a wavelength of 382 nm, light intensity of 50 mW / cm 2 UV light, irradiation for 18 min, to obtain the first polymer composite liquid crystal layer and polymer transparent layer;

[0174] 2) Preparation of the second polymer composite liquid crystal layer

[0175] The nematic liquid crystal, voltage toner mixture, UV polymerizable monomer mixture, photoinitiator mixture, UV absorber and micron-sized spherical spacer are mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture;

[0176] The liquid crystal / UV polymerizable monomer mixture is as follows:

[0177] 75 parts of nematic liquid crystal;

[0178] 20 parts of voltage toner mixture: 4 parts of (R)-(-)-2-pentanol, 4 parts of (R)-2-chlorobutyric acid, 3 parts of (R)-3-hydroxybutyric acid methyl ester, 3 parts of (S)-(+)-2-butanol, 3 parts of (S)-2-chloro-3-methylbutyric acid and 3 parts of (S)-2-chloro-4-methylvaleric acid;

[0179] 40 parts of UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 4 parts of dibromophenyl glycidyl ether, 4 parts of polydi-pentaerythritol hexaacrylate, 4 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 4 parts of neopentyl glycol polymethylol polyethylene oxide diacrylate, 4 parts of cyclotrimethylolpropane formal acrylate;

[0180] 3 parts of photoinitiator mixture: 0.6 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0.6 parts of ethyl-p-dimethylaminobenzoate, 0.6 parts of benzophenone, 0.6 parts of triphenylsulfonium hexafluorophosphate, 0.6 parts of tetraethyl Michler's ketone;

[0181] 0.5 parts of UV absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.1 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.2 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0182] 0.5 parts micron-sized spherical spacers: 0.1 parts cross-linked polyacrylic acid microspheres, 0.1 parts cross-linked polymethyl methacrylate microspheres, 0.1 parts cross-linked PEG microspheres, 0.1 parts silica microspheres, and 0.1 parts alumina microspheres.

[0183] A 8-μm-thick liquid crystal / UV-polymerizable monomer mixture was uniformly coated on the other side of the polymer transparent layer at 31°C under vacuum by means of doctor blading (5 cm·s -1 ) and then a second PET transparent film was attached to the surface of the liquid crystal / UV-polymerizable monomer mixture. The second polymer composite liquid crystal layer was obtained by irradiation with UV light having a wavelength of 382 nm and an illumination intensity of 50 mW / cm 2 for 18 min.

[0184] Example 5:

[0185] 1) Preparation of the first polymer composite liquid crystal layer and the polymer transparent layer

[0186] The nematic liquid crystal, the voltage toner mixture, the UV-polymerizable monomer mixture, the photoinitiator mixture, the UV absorber, and the micron-sized spherical spacers were mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV-polymerizable monomer mixture:

[0187] The liquid crystal / UV-polymerizable monomer mixture had the following composition:

[0188] 80 parts nematic liquid crystal;

[0189] 20 parts voltage toner mixture: 4 parts (R)-(-)-2-pentanol, 4 parts (R)-2-chlorobutyric acid, 3 parts (R)-3-hydroxybutyric acid methyl ester, 3 parts (S)-(+)-2-butanol, 3 parts (S)-2-chloro-3-methylbutyric acid, and 3 parts (S)-2-chloro-4-methylvaleric acid;

[0190] 47 parts UV-polymerizable monomer mixture: 5 parts trimethylolpropane triglycidyl ether, 5 parts resorcinol diglycidyl ether, 5 parts 4-tert-butylphenyl glycidyl ether, 5 parts neopentyl glycol diglycidyl ether, 5 parts dibromomethylphenyl glycidyl ether, 5 parts polydipentaerythritol hexaacrylate, 5 parts α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 6 parts neopentyl glycol polymethyloxetane diacrylate, 6 parts cyclotrimethylolpropane formal acrylate;

[0191] 6 parts of photoinitiator mixture: 1.2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 1.2 parts of ethyl p-dimethylaminobenzoate, 1.2 parts of benzophenone, 1.2 parts of triphenylsulfonium hexafluorophosphate, 1.2 parts of tetraethyl Michler's ketone;

[0192] 0.7 parts of ultraviolet absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.2 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.3 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0193] 0.5 parts of micron-sized spherical spacers: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0194] The first layer of PET transparent film was uniformly coated with a 10-μm-thick liquid crystal / ultraviolet-polymerizable monomer mixture on the conductive surface by means of scraping (7 cm·s -1 ) at 33°C under vacuum, and after coating, it was left to stand for 20 min to allow phase separation to occur. Then, it was irradiated with ultraviolet light having a wavelength of 388 nm and an illumination intensity of 67 mW / cm 2 for 20 min to obtain a first polymer composite liquid crystal layer and a polymer transparent layer.

[0195] 2) Preparation of a second polymer composite liquid crystal layer

[0196] The nematic liquid crystal, voltage toner mixture, ultraviolet-polymerizable monomer mixture, photoinitiator mixture, ultraviolet absorber, and micron-sized spherical spacers were mixed in the following weight proportions to obtain a uniform and stable liquid crystal / ultraviolet-polymerizable monomer mixture.

[0197] The liquid crystal / ultraviolet-polymerizable monomer mixture had the following proportions

[0198] 80 parts of nematic liquid crystal;

[0199] 25 parts of voltage toner mixture: 5 parts of (R)-(-)-2-pentanol, 4 parts of (R)-2-chlorobutyric acid, 4 parts of (R)-methyl 3-hydroxybutyrate, 4 parts of (S)-(+)-2-butanol, 4 parts of (S)-2-chloro-3-methylbutyric acid, and 4 parts of (S)-2-chloro-4-methylvaleric acid;

[0200] 42 parts of UV polymerizable monomer mixture: 4 parts of trimethylolpropane triglycidyl ether, 4 parts of resorcinol diglycidyl ether, 4 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydi-pentaerythritol hexaacrylate, 5 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-poly(ethylene oxide), 5 parts of neopentyl glycol polymethyloxetane diacrylate, 5 parts of cyclotrimethylolpropane formal acrylate;

[0201] 6 parts of photoinitiator mixture: 1.2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 1.2 parts of ethyl-p-dimethylaminobenzoate, 1.2 parts of benzophenone, 1.2 parts of triphenylsulfonium hexafluorophosphate, 1.2 parts of tetraethyl Michler's ketone;

[0202] 0.7 parts of UV absorber: 0.2 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.3 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.2 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0203] 0.5 parts of micron-sized spherical spacers: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0204] A 10-μm-thick liquid crystal / UV polymerizable monomer mixture was uniformly coated on the other side of the polymer transparent layer at 33°C under vacuum by means of doctor blading (7 cm·S -1 ) and, after the coating was completed, a second PET transparent film was attached to the surface of the liquid crystal / UV polymerizable monomer mixture, which was irradiated with UV light having a wavelength of 388 nm and an illumination intensity of 67 mW / cm 2 for 20 min to obtain a second polymer composite liquid crystal layer.

[0205] Example 6:

[0206] 1) Preparation of a first polymer composite liquid crystal layer and a polymer transparent layer

[0207] The nematic liquid crystal, voltage toner mixture, UV polymerizable monomer mixture, photoinitiator mixture, UV absorber, and micron-sized spherical spacers were mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0208] Liquid crystal / UV polymerizable monomer mixture ratio is as follows:

[0209] 85 parts of nematic liquid crystal;

[0210] 25 parts of voltage tinting mixture: 4 parts of (R)-(-)-2-pentanol, 4 parts of (R)-2-chlorobutyric acid, 4 parts of (R)-methyl 3-hydroxybutyrate, 4 parts of (S)-(+)-2-butanol, 4 parts of (S)-2-chloro-3-methylbutyric acid, and 5 parts of (S)-2-chloro-4-methylvaleric acid;

[0211] 49 parts of UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 6 parts of polydi-pentaerythritol hexaacrylate, 6 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-poly(ethylene oxide, 6 parts of neopentyl glycol polymethyloxetane diacrylate, 6 parts of cyclotrimethylolpropane formal acrylate;

[0212] 8 parts of photoinitiator mixture: 1.6 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 1.6 parts of ethyl p-dimethylaminobenzoate, 1.6 parts of benzophenone, 1.6 parts of triphenylsulfonium hexafluorophosphate, 1.6 parts of tetraethyl Michler's ketone;

[0213] 0.8 parts of UV absorber: 0.25 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.25 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.3 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0214] 0.5 parts of micron-sized spherical spacers: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0215] A 13-μm-thick liquid crystal / UV polymerizable monomer mixture was uniformly coated on the conductive surface of the first layer of PET transparent film at 34°C under vacuum by means of doctor blade (9 cm·S -1 ) and, after coating, was allowed to stand for 25 min to wait for phase separation. UV light with a wavelength of 393 nm and an illumination intensity of 84 mW / cm 2 was used to irradiate for 25 min, resulting in a first polymer composite liquid crystal layer and a polymer transparent layer;

[0216] 2) Preparation of the second polymer composite liquid crystal layer

[0217] A nematic liquid crystal, a voltage tinting agent mixture, a UV polymerizable monomer mixture, a photoinitiator mixture, a UV absorber, and a micron-sized spherical spacer were mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0218] The liquid crystal / UV polymerizable monomer mixture was, for example, as follows:

[0219] 85 parts of a nematic liquid crystal;

[0220] 28 parts of a voltage tinting agent mixture: 5 parts of (R)-(-)-2-pentanol, 5 parts of (R)-2-chlorobutyric acid, 5 parts of (R)-3-hydroxybutyric acid methyl ester, 5 parts of (S)-(+)-2-butanol, 4 parts of (S)-2-chloro-3-methylbutyric acid, and 4 parts of (S)-2-chloro-4-methylvaleric acid;

[0221] 45 parts of a UV polymerizable monomer mixture: 5 parts of trimethylolpropane triglycidyl ether, 5 parts of resorcinol diglycidyl ether, 5 parts of 4-tert-butylphenyl glycidyl ether, 5 parts of neopentyl glycol diglycidyl ether, 5 parts of dibromophenyl glycidyl ether, 5 parts of polydipentaerythritol hexaacrylate, 5 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-propenoyl)oxy]-polyoxirane, 5 parts of neopentyl glycol polymethyloxirane diacrylate, 5 parts of cyclotrimethylolpropane formal acrylate;

[0222] 8 parts of a photoinitiator mixture: 1.6 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 1.6 parts of ethyl-p-dimethylaminobenzoate, 1.6 parts of benzophenone, 1.6 parts of triphenylsulfonium hexafluorophosphate, 1.6 parts of tetraethyl Michler's ketone;

[0223] 0.8 parts of a UV absorber: 0.25 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.3 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.25 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0224] 0.5 parts of a micron-sized spherical spacer: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0225] A liquid crystal / UV polymerizable monomer mixture was prepared by mixing the following components at 34°C under vacuum conditions using a doctor blade (9 cm x S-1 ) in the same manner as the first polymer composite liquid crystal layer, and then a second PET transparent film was attached to the surface of the liquid crystal / UV polymerizable monomer mixture. The second polymer composite liquid crystal layer was obtained by irradiation with UV light having a wavelength of 393 nm and an illumination intensity of 84 mW / cm2for 25 min. 2

[0226] Example 7:

[0227] 1) Preparation of the first polymer composite liquid crystal layer and the polymer transparent layer

[0228] A nematic liquid crystal, a voltage toner mixture, a UV polymerizable monomer mixture, a photoinitiator mixture, a UV absorber, and a micron-sized spherical spacer were mixed in the following weight parts to obtain a uniform and stable liquid crystal / UV polymerizable monomer mixture:

[0229] The liquid crystal / UV polymerizable monomer mixture was, for example, as follows:

[0230] 95 parts of a nematic liquid crystal;

[0231] 25 parts of a voltage toner mixture: 4 parts of (R)-(-)-2-pentanol, 4 parts of (R)-2-chlorobutyric acid, 4 parts of (R)-3-hydroxybutyric acid methyl ester, 4 parts of (S)-(+)-2-butanol, 4 parts of (S)-2-chloro-3-methylbutyric acid, and 5 parts of (S)-2-chloro-4-methylvaleric acid;

[0232] 50 parts of a UV polymerizable monomer mixture: 6 parts of trimethylolpropane triglycidyl ether, 6 parts of resorcinol diglycidyl ether, 6 parts of 4-tert-butylphenyl glycidyl ether, 6 parts of neopentyl glycol diglycidyl ether, 6 parts of dibromophenyl glycidyl ether, 6 parts of polydi-pentaerythritol hexaacrylate, 6 parts of α,α'-[(1-methylethylidene)bis-4,1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyoxirane, 4 parts of neopentyl glycol polymethyloloxirane dipropenoate, 4 parts of cyclotrimethylolpropane methylal propenoate;

[0233] 10 parts of a photoinitiator mixture: 2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 2 parts of ethyl p-dimethylaminobenzoate, 2 parts of benzophenone, 2 parts of triphenylsulfonium hexafluorophosphate, 2 parts of tetraethyl Michler's ketone;

[0234] ​1 part of ultraviolet absorber: 0.3 part of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.3 part of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.4 part of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0235] 0.5 part of micron-sized spherical spacers: 0.1 part of crosslinked polyacrylic acid microspheres, 0.1 part of crosslinked polymethyl methacrylate microspheres, 0.1 part of crosslinked PEG microspheres, 0.1 part of silica microspheres, and 0.1 part of alumina microspheres.

[0236] At 35°C, under vacuum conditions, a 15-μm-thick liquid crystal / ultraviolet-polymerizable monomer mixture was uniformly coated on the conductive surface of the first layer of PET transparent film by means of doctor blading (10 cm·S -1 ) and, after coating, was allowed to stand for 30 min to wait for phase separation to occur. Then, using ultraviolet light with a wavelength of 398 nm and an illumination intensity of 100 mW / cm 2 , the mixture was irradiated for 30 min to obtain a first polymer composite liquid crystal layer and a polymer transparent layer.

[0237] 2) Preparation of a second polymer composite liquid crystal layer

[0238] The nematic liquid crystal, the voltage toner mixture, the ultraviolet-polymerizable monomer mixture, the photoinitiator mixture, the ultraviolet absorber, and the micron-sized spherical spacers were mixed in the following weight proportions to obtain a uniformly stable liquid crystal / ultraviolet-polymerizable monomer mixture:

[0239] The liquid crystal / ultraviolet-polymerizable monomer mixture had the following proportions by weight:

[0240] 95 parts of nematic liquid crystal;

[0241] 30 parts of voltage toner mixture: 5 parts of (R)-(-)-2-pentanol, 5 parts of (R)-2-chlorobutyric acid, 5 parts of (R)-3-hydroxybutyric acid methyl ester, 5 parts of (S)-(+)-2-butanol, 5 parts of (S)-2-chloro-3-methylbutyric acid, and 5 parts of (S)-2-chloro-4-methylvaleric acid;

[0242] 50 parts of UV polymerizable monomer mixture: 6 parts of trimethylolpropane triglycidyl ether, 6 parts of resorcinol diglycidyl ether, 6 parts of 4-tert-butylphenyl glycidyl ether, 6 parts of neopentyl glycol diglycidyl ether, 6 parts of dibromophenyl glycidyl ether, 5 parts of polydi-pentaerythritol hexaacrylate, 5 parts of α, α'-[(1-methylethylidene)bis-4, 1-phenylene]bis[ω-[(2-propenoyl)oxy]-polyethylene oxide, 5 parts of neopentyl glycol polymethyloxetane diacrylate, 5 parts of cyclotrimethylolpropane formal acrylate;

[0243] 10 parts of photoinitiator mixture: 2 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 2 parts of ethyl-p-dimethylaminobenzoate, 2 parts of benzophenone, 2 parts of triphenylsulfonium hexafluorophosphate, 2 parts of tetraethyl Michler's ketone;

[0244] 1 part of UV absorber: 0.3 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (CAS No.: 3896-11-5), 0.4 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenol (CAS No.: 3864-99-1), 0.3 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole;

[0245] 0.5 parts of micron-sized spherical spacers: 0.1 parts of crosslinked polyacrylic acid microspheres, 0.1 parts of crosslinked polymethyl methacrylate microspheres, 0.1 parts of crosslinked PEG microspheres, 0.1 parts of silica microspheres, and 0.1 parts of alumina microspheres.

[0246] The polymer transparent layer is coated with a 15 μm thick layer of liquid crystal / UV polymerizable monomer mixture on the other side at 35°C under vacuum conditions by means of scraping (10 cm·S -1 ) and then a second PET transparent film is attached to the surface of the liquid crystal / UV polymerizable monomer mixture, which is irradiated with UV light of wavelength 398 nm and light intensity 100 mW / cm 2 for 30 min to obtain a second polymer composite liquid crystal layer.

[0247] Example 2:

[0248] The liquid crystal writing board provided by the present application comprises the liquid crystal writing device for dual-color writing display as described in the present application.

[0249] Example 3:

[0250] The liquid crystal blackboard provided by the present application comprises the liquid crystal writing device for dual-color writing display as described in the present application.

[0251] Embodiment 4:

[0252] The embodiment 4 of the present application provides a liquid crystal writing board, which comprises the liquid crystal writing device for dual-color writing display as described in the embodiment 1 of the present application.

[0253] The above only provides the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A liquid crystal writing device for dual-color writing display, characterized in that: it comprises a first PET transparent film, a first polymer composite liquid crystal coating, a polymer transparent layer, a second polymer composite liquid crystal coating and a second PET transparent film arranged in layers; the polymer transparent layer is formed by phase separation of monomers with small density and monomers with large density in the first polymer composite liquid crystal coating after light curing; the first side of the first PET transparent film is plated with ITO, and the second side of the second PET transparent film is plated with ITO; the first polymer composite liquid crystal coating and the second polymer composite liquid crystal coating both contain voltage colorants of left-handed and right-handed, and the driving voltage and driving frequency of the two liquid crystal layers are kept the same or different by adjusting the content of ultraviolet polymerizable monomers, voltage colorants and nematic liquid crystals in the liquid crystal layer; the raw material composition of the voltage colorant mixture comprises 0-10 parts of (R)-(-)-2-pentanol, 0-10 parts of (R)-2-chlorobutyric acid, 0-10 parts of (R)-3-hydroxybutyric acid methyl ester, 0-10 parts of (S)-(+)-2-butanol, 0-10 parts of (S)-2-chloro-3-methylbutyric acid and 0-10 parts of (S)-2-chloro-4-methylvaleric acid, and each component is not zero at the same time. 2.The liquid crystal writing device for dual-color writing display according to claim 1, characterized in that: the first polymer composite liquid crystal coating is uniformly distributed on the ITO of the first PET transparent film by means of blade coating, and the second polymer composite liquid crystal coating is uniformly distributed on the ITO of the second PET transparent film by means of blade coating. 3.The liquid crystal writing device for dual-color writing display according to claim 1, characterized in that: the first PET transparent film and the second PET transparent film are doped with infrared light shielding materials, and the infrared light shielding materials comprise 0-10 parts of zinc oxide nanospheres, 0-10 parts of gold sulfide nanospheres and 0-10 parts of copper oxide nanorods. 4.The liquid crystal writing device for dual-color writing display according to claim 1, characterized in that: the raw material composition of the first polymer composite liquid crystal coating comprises 50-95 parts of nematic liquid crystal, 1-30 parts of voltage colorant mixture, 5-50 parts of ultraviolet polymerizable monomer mixture, 0.1-10 parts of photoinitiator mixture, 0.01-1 parts of ultraviolet absorber and 0.05-0.5 parts of micron-sized spherical spacers. 5.The liquid crystal writing device for dual-color writing display according to claim 4, characterized in that: ​ ​ ​ ​ ​ ​ ​ The raw material composition of the ultraviolet polymerizable monomer mixture includes, by weight fraction: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of dibromomethylphenyl glycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, 0-30 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-propenoyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethylol polyethylene oxide diacrylate, 0-30 parts of cyclotrimethylolpropane formal acrylate, and each component is not 0 at the same time.

6. The liquid crystal writing device for dual color writing display according to claim 4, wherein: The composition of the photoinitiator mixture includes, by weight fraction: 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, and each component is not 0 at the same time.

7. The liquid crystal writing device for dual color writing display according to claim 4, wherein: The raw material composition of the ultraviolet absorber includes, by weight fraction: 0-1 part of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0-1 part of 2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol, 0-1 part of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and each component is not 0 at the same time.

8. The liquid crystal writing device for dual color writing display according to claim 4, wherein: The micron-sized spherical spacers include: 0-0.5 parts of cross-linked polyacrylic acid microspheres, 0-0.5 parts of cross-linked polymethyl methacrylate microspheres, 0-0.5 parts of cross-linked PEG microspheres, 0-0.5 parts of silica microspheres, and 0-0.5 parts of alumina microspheres, and each micron-sized spherical spacer is not 0 at the same time.

9. The liquid crystal writing device for dual-color writing display according to claim 1, wherein: The raw material composition of the second polymer composite liquid crystal coating includes, by weight fraction: 50-95 parts of nematic liquid crystal, 1-30 parts of voltage toner mixture, 5-50 parts of ultraviolet polymerizable monomer mixture, 0.1-10 parts of photoinitiator mixture, 0.01-1 parts of ultraviolet absorber, and 0.05-0.5 parts of micron-sized spherical spacers.

10. The liquid crystal writing device for dual-color writing display according to claim 9, wherein: The raw material composition of the ultraviolet polymerizable monomer mixture includes, by weight fraction: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of dibromomethylphenyl glycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, 0-30 parts of alpha, alpha'-[(1-methylethylidene)bis-4,1-phenylene]bis[omega-[(2-propenoyl)oxy]-polyethylene oxide, 0-30 parts of neopentyl glycol polymethylol polyethylene oxide diacrylate, 0-30 parts of cyclotrimethylolpropane formal acrylate, and each component is not 0 at the same time.

11. The liquid crystal writing device for dual color writing display according to claim 9, wherein: The composition of the photoinitiator mixture comprises, by weight fraction: 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl-p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, and each component is not 0 at the same time.

12. The liquid crystal writing device for dual color writing display according to claim 9, wherein: The raw material composition of the ultraviolet absorber comprises, by weight fraction: 0-1 parts of 2'-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 0-1 parts of 2,4-di-tert-butyl-6-(5-chlorobenzotriazole-2-yl)phenol, 0-1 parts of 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, and each component is not 0 at the same time.

13. The liquid crystal writing device for dual color writing display according to claim 9, wherein: The micron-sized spherical spacers are 0-0.5 parts of cross-linked polyacrylic acid microspheres, 0-0.5 parts of cross-linked polymethyl methacrylate microspheres, 0-0.5 parts of cross-linked PEG microspheres, 0-0.5 parts of silica microspheres, and 0-0.5 parts of alumina microspheres, and each micron-sized spherical spacer is not 0 at the same time.

14. The liquid crystal writing device for dual-color writing display according to claim 1, characterized in that: The raw material composition of the polymer transparent layer comprises, by weight fraction: 5-50 parts of an ultraviolet polymerizable monomer mixture and 0.1-10 parts of a photoinitiator mixture.

15. The liquid crystal writing device for dual-color writing display according to claim 14, characterized in that: The composition of the ultraviolet polymerizable monomer mixture comprises, by weight fraction: 0-30 parts of trimethylolpropane triglycidyl ether, 0-30 parts of resorcinol diglycidyl ether, 0-30 parts of 4-tert-butylphenyl glycidyl ether, 0-30 parts of neopentyl glycol diglycidyl ether, 0-30 parts of polydi-pentaerythritol hexaacrylate, and 0-30 parts of neopentyl glycol polymethyloxetane diacrylate, and each component is not 0 at the same time.

16. The liquid crystal writing device for two-color writing display according to claim 14, wherein: The composition of the photoinitiator mixture comprises, by weight fraction: 0-10 parts of 2-hydroxy-2-methyl-1-[4-(tert-butyl)phenyl]-1-propanone, 0-10 parts of ethyl-p-dimethylaminobenzoate, 0-10 parts of benzophenone, 0-10 parts of triphenylsulfonium hexafluorophosphate, 0-10 parts of tetraethyl Michler's ketone, and each component is not 0 at the same time.

17. A liquid crystal writing board, characterized in that: It comprises the liquid crystal writing device for dual-color writing display according to any one of claims 1-16.

18. A liquid crystal blackboard, characterized in that: It comprises the liquid crystal writing device for dual-color writing display according to any one of claims 1-16.

19. A liquid crystal drawing board, characterized in that: It comprises the liquid crystal writing device for dual-color writing display according to any one of claims 1-16.

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